Method for producing antireflection film-coated plastic lens, and antireflection film-coated plastic lens

ABSTRACT

The method produces a plastic lens with an antireflection film which have the advantages of good adhesion of the antireflection film to any type of hard coat film that underlies it and good abrasion resistance and provides a plastic lens with an antireflection film. The method includes the steps of applying water or an aqueous solution to a plastic lens with an organosilicon compound-containing hard coat film to form a liquid film of water or the aqueous solution on the surface of the hard coat film, then allowing ozone gas to contact with the liquid film to treat the surface of the hard coat film with the ozone gas, and thereafter forming an antireflection film on the surface of the hard coat film through vapor deposition.

FIELD OF THE INVENTION

[0001] The present invention relates to a method for producing a plasticlens with an antireflection film and to a plastic lens with anantireflection film. More precisely, the invention relates to a methodof producing a plastic lens having the advantages of good adhesion ofthe antireflection film to the hard coat film that underlies theantireflection film and good abrasion resistance, and to a plastic lens.

BACKGROUND OF THE INVENTION

[0002] To prevent the deterioration of adhesion between a hard coat filmand an antireflection film of a plastic lens and abrasion resistancethereof, it is known to treat the surface of the hard coat film withoxygen radicals, that is, with ozone gas or ozone water. One example ofthe method of producing such a plastic lens is disclosed inJP-A-2001-141905, in which the surface of a hard coat film of a plasticlens substrate with a hard coat film containing titanium oxide fineparticles is treated with ozone gas or dipped into ozone water and thenan antireflection film is formed on the treated hard coat film throughvapor deposition.

[0003] However, when the hard coat film formed on a plastic lenssubstrate contains metal oxide particles other than titanium oxideparticles, such as silicon oxide particles, and when its surface istreated with ozone gas or ozone water according to this prior artmethod, there is a probability that the adhesion of the hard coat filmto the antireflection film that overlies it and also the abrasionresistance of the thus-coated plastic lenses inevitably deteriorate.

SUMMARY OF THE INVENTION

[0004] This invention provides a method for producing a plastic lenswith an antireflection film having good adhesion of the antireflectionfilm to any type of hard coat film that underlies it and good abrasionresistance, and provides a plastic lens with an antireflection film.

[0005] This invention involves forming a liquid film of water or anaqueous solution on the surface of the hard coat film of a plastic lensbefore an antireflection film is formed on the hard coat film, followedby treating the film with ozone gas. Specifically, the inventionprovides a method for producing a plastic lens with an antireflectionfilm, which comprises applying water or an aqueous solution to a plasticlens with an organosilicon compound-containing hard coat film to form aliquid film of water or the aqueous solution on the surface of the hardcoat film, allowing ozone gas to contact with the liquid film to treatthe surface of the hard coat film with the ozone gas, and thereafterforming the antireflection film on the surface of the hard coat filmthrough vapor deposition, and provides a plastic lens with anantireflection film obtained by this production method.

[0006] The method for producing the plastic lens with the antireflectionfilm of the invention includes applying water or an aqueous solution toa plastic lens with an organosilicon compound-containing hard coat filmto form a liquid film of water or the aqueous solution on the surface ofthe hard coat film, allowing ozone gas to contact with the liquid filmto treat the surface of the hard coat film with the ozone gas, andthereafter forming an antireflection film on the treated surface of thehard coat film by vapor deposition. The production method of theinvention provides a plastic lens with an antireflection film which hasthe advantages of good abrasion resistance and good adhesion of theantireflection film to any type of hard coat film that underlies it.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007]FIG. 1 shows an ozone gas-treating apparatus for carrying out themethod of the invention of producing a plastic lens with anantireflection film.

[0008]FIG. 2 shows an ozone-treating tank in the ozone gas-treatingapparatus for carrying out the method of the invention of producing aplastic lens with an antireflection film.

DETAILED DESCRIPTION OF THE INVENTION

[0009] Examples of the lens production method of the invention and theapparatus for carrying out this method are described in detail hereafterwith reference to the drawings attached hereto.

[0010]FIG. 1 shows an ozone-treating apparatus 1 for use in performingthe method of the invention, which basically comprises a known ozone gasgenerator 2; an ozone gas-feeding duct 2 a; an ozone-treating tank 3 forcontacting ozone gas with the surface of a hard coat film on a lens; anaqueous ozone waste-decomposing unit 4; a post-treating unit 5 forperforming treatments such as drying of the lens; an ozonegas-decomposing unit 6; a solution-feeding duct 7; and an ejection tube8 through which ozone gas is ejected toward the lens in theozone-treating tank 3.

[0011]FIG. 2 shows the ozone-treating tank 3, which basically comprisesa space 3 a in which water is applied to the hard coat film of the lens9 to form a water film thereon and ozone gas is applied to the lens withthe water film on it; a solution pool 3 b arranged in the lower part ofthe ozone-treating tank 3 and having the ejection tube therein; and aholder 3 c for holding the lens.

[0012] The ozone-treating apparatus 1 operates as follows. As shown inFIG. 2, the solution in the solution pool 3 b is pumped to spray nozzle10 via a circulation duct 11 a by pump 11. At that time, the solution issprayed through the spray nozzle 10 onto the hard coat film of the lens9 to form a film of the solution. The sprayed solution that drips fromthe lens surface is pooled in the solution pool 3 b, and may becirculated and reused. The amount of the solution spray to be applied tothe lens is preferably from 0.3 to 3.5 liters/min, for example, when thevolume (of the vapor part) of the treating tank 3 is about 120 liters.

[0013] The solution in the solution pool 3 b is preferably water, ozonewater, or an aqueous solution that contains a radical scavenger. Theradical scavenger may be any known one, including, for example, hydrogencarbonates such as sodium hydrogen carbonate, and phosphates such assodium phosphate. The concentration of the radical scavenger in thesolution is preferably from 0.01 mols/liter up to a saturatedconcentration thereof, more preferably from 0.1 mols/liter to 1.00mol/liter, in view of the adhesion of the hard coat film to theantireflection film. Preferably, the temperature of the solution pool 3b falls between about 15° C. and about 30° C.

[0014] The ozone gas generator 2 generates ozone gas. Thus generated,the ozone gas moves to the ejection tube 8 which has orifices formedtherein, via the feeding duct 2 a, and then this ozone gas is ejectedout into the ozone-treating tank 3 through the orifices. In this stage,the flow rate of the ozone gas that is fed through the feeding duct 2 ais preferably from 2 to 3 liters/min, for example, when the volume (ofthe vapor part) of the treating tank 3 is about 120 liters. Thoughdepending on the type of the hard coat film of the lens and on the typeof the antireflection film to be formed thereon, the ozone gasconcentration to be fed through the feeding duct 2 a is generally 50g/Nm³ or more, preferably 100 g/Nm³ or more, more preferably 140 g/Nm³or more for attaining good adhesion of the hard coat film to theantireflection film. Preferably, the temperature of the ozone gas to befed falls between 15 and 40° C.

[0015] The ozone gas ejected out through the ejection tube 8 is allowedto come into contact with the solution pool 3 b of the ozone-treatingtank 3. The ozone gas thus allowed to contact the solution pool 3 bfirst dissolves in the solution in the solution pool 3 b, but after ithas reached the saturation point, it does not dissolve further in thesolution and moves upward and is brought into contact with the lenses 9.Based on this principle, the liquid film of the lens 9 is treated withozone gas. The treating time preferably falls between 10 seconds and 10minutes, though varying depending on the ozone gas concentration and thecomposition of the hard coat film. If the treating time is too long, thehard coat film may peel off. Therefore, the treatment is carried out tosuch a degree that the hard coat film does not peel because thetreatment time is too long.

[0016] When it is not necessary to use the solution in the solution pool3 b any more, it is led to the aqueous ozone waste-decomposing unit 4via a transfer duct 4 a, and processed therein. The ozone gas in thetreating tank is led to the ozone-decomposing unit 6 via ozone gastransfer duct 6 a, and is then discharged out of the apparatus. When afresh solution is needed, it is fed into the solution pool 3 via thesolution-feeding duct 7.

[0017] The organosilicon compound used to form the hard coat film is,for example, at least one selected from compounds of general formula(I):

(R¹)_(a)(R³ )_(b)Si(OR²)_(4−(a+b))   (I)

[0018] wherein R¹ and R³ each independently represent a monovalenthydrocarbon group having from 1 to 10 carbon atoms, with or without afunctional group; R² represents an alkyl group having from 1 to 8 carbonatoms, an aryl group having from 6 to 10 carbon atoms, an aralkyl grouphaving from 7 to 10 carbon atoms or an acyl group having from 1 to 8carbon atoms; a and b each independently indicate 0 or 1; and aplurality of the OR² groups may be the same or different from eachother, and compounds of general formula (II):

[0019] wherein R⁴ and R⁵ each independently represent a monovalenthydrocarbon group having from 1 to 5 carbon atoms, with or without afunctional group; X¹ and X² each independently represent an alkyl grouphaving from 1 to 4 carbon atoms or an acyl group having from 1 to 4carbon atoms; Y represents a divalent hydrocarbon group having from 1 tocarbon atoms; x and y each independently indicate 0 or 1; a plurality ofthe X¹ groups may be the same or different from each other; and aplurality of the X² groups may be the same or different from each other,and hydrolyzates of the compounds of formula (I) and formula (II).

[0020] In formula (I), the monovalent hydrocarbon group having from 1 to10 carbon atoms for R¹ and R³ includes an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 6 to 10 carbon atoms, and an aralkyl group havingfrom 7 to 10 carbon atoms. The alkyl and alkenyl groups may be linear,branched or cyclic. Examples of the alkyl group having from 1 to 10carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, cyclopentyl andcyclohexyl groups. Examples of the alkenyl group having from 2 to 10carbon atoms include vinyl, allyl, butenyl, hexenyl and octenyl groups.Examples of the aryl group having from 6 to 10 carbon atoms includephenyl, tolyl, xylyl and naphthyl groups. Examples of the aralkyl grouphaving from 7 to 10 carbon atoms include benzyl, phenethyl andnaphthyhnethyl groups.

[0021] These hydrocarbon groups may have a functional group introducedthereinto. These functional group include, for example, a halogen atom,a glycidoxy group, an epoxy group, an amino group, a cyano group, amercapto group, and a (meth)acryloxy group. Examples of the monovalenthydrocarbon group having from 1 to 10 carbon atoms with such afunctional group include glycidoxymethyl, α-glycidoxyethyl,β-glycidoxyethyl, α-glycidoxypropyl, β-glycidoxypropyl,γ-glycidoxypropyl, α-glycidoxybutyl, β-glycidoxybutyl, γ-glycidoxybutyl,δ-glycidoxybutyl, (3,4-epoxycyclohexyl)methyl,β-(3,4-epoxycyclohexyl)ethyl, γ-(3,4-epoxycyclohexyl)propyl,δ-(3,4-epoxycyclohexyl)butyl, chloromethyl, γ-chloropropyl,3,3,3-trifluoropropyl, γ-methacryloxypropyl, γ-acryloxypropyl,γ-mercaptopropyl, ⊖-cyanoethyl, N-(β-aminoethyl)-γ-aminopropyl andγ-aminopropyl groups.

[0022] On the other hand, the alkyl group having from 1 to 8 carbonatoms for R² may be linear, branched or cyclic. Examples thereof includemethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl, hexyl, cyclopentyl and cyclohexyl groups. Examplesof the aryl group having from 6 to 10 carbon atoms for R² includephenyl, tolyl and xylyl groups; and examples of the aralkyl group havingfrom 7 to 10 carbon atoms for R² include benzyl and phenethyl groups.The acyl group having from 1 to 8 carbon atoms for R² is, for example,an acetyl group.

[0023] Examples of the compounds of formula (I) include methyl silicate,ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate,sec-butyl silicate, tert-butyl silicate, tetraacetoxysilane,methyltrimethoxysilane, methyltripropoxysilane, methyltrimethoxysilane,methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane,methyltribenzyloxysilane, methyltriphenethyloxysilane,glycidoxymethyltriethoxysilane, glycidoxymethyltrimethoxysilane,α-glycidoxyethyltrimethoxysilane, α-glycidoxypropyltrimethoxysilane,β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane,α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane,β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane,γ-glycidoxypropyltriphenoxysilane, β-glycidoxybutyltrimethoxysilane,β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane,γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane,δ-glycidoxybutyltriethoxysilane,(3,4-epoxycyclohexyl)methyltriethoxysilane,(3,4-epoxycyclohexyl)methyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltripropoxysilane,β-(3,4-epoxycyclohexyl)ethyltributoxysilane,β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane,δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane,δ-(3,4-epoxycyclohexyl)butyltriethoxysilane,glycidoxymethylmethyldimethoxysilane,glycidoxymethylmethyldiethoxysilane,α-glycidoxyethylmethyldimethoxysilane,α-glycidoxyethylmethyldiethoxysilane,β-glycidoxyethylmethyldimethoxysilane,β-glycidoxyethylmethyldiethoxysilane,α-glycidoxypropylmethyldimethoxysilane,α-glycidoxypropylmethyldiethoxysilane,β-glycidoxypropyhmethyldimethoxysilane,α-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldipropoxysilane,γ-glycidoxypropylmethyldibutoxysilane,γ-glycidoxypropylmethyldiphenoxysilane,γ-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropylethyldiethoxysilane,γ-glycidoxypropylvinyldimethoxysilane,γ-glycidoxypropylvinyldiethoxysilane,γ-glycidoxypropylphenyldimethoxysilane,γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane,vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane,γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane,chloromethyltrimethoxysilane, chloromethyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldimethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane,dimnethyldimethoxysilane, phenylmethyldimethoxysilane,dimethyldiethoxysilane, phenylmethyldiethoxysilane,γ-chloropropylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane,dimethyldiacetoxysilane, y-methacryloxypropylmethylditnethoxysilane,γ-methacryloxypropyhnethyldiethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, methylvinyldiimethoxysilane, andmethylvinyldiethoxysilane.

[0024] On the other hand, in formula (II), the alkyl group having from 1to 4 carbon atoms for X¹ and X² includes methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups; and theacyl group having from 1 to 4 carbon atoms is, for example, preferablyan acetyl group. These X¹ and X² may independently be the same ordifferent from each other.

[0025] The monovalent hydrocarbon group having from 1 to 5 carbon atomsfor R⁴ and R⁵ includes an alkyl group having from 1 to 5 carbon atoms,and an alkenyl group having from 2 to 5 carbon atoms. These may belinear or branched. Examples of the alkyl group include methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and pentyl groups.Examples of the alkenyl group include vinyl, allyl and butenyl groups.These hydrocarbon groups may have a functional group introducedthereinto. For the functional group and the functional group-havinghydrocarbon group, those mentioned hereinabove for R¹ and R³ in formula(I) are exemplified. These R⁴ and R⁵ may be the same or different fromeach other.

[0026] For the divalent hydrocarbon group having from 1 to 20 carbonatoms for Y, an alkylene group and an alkylidene group are preferred andexamples thereof include, for example, methylene, ethylene, propylene,butylene, pentylene, hexylene, octylene, ethylidene and propylidenegroups.

[0027] Examples of the compounds of formula (II) includemethylenebis(methyldimethoxysilane), ethylenebis(ethyldimethoxysilane),propylenebis(ethyldiethoxysilane), andbutylenebis(methyldiethoxysilane).

[0028] The organosilicon compound to be contained in the hard coat filmin the invention may be one selected from the compounds of formulas (I)and (II) and their hydrolyzates, or may be a combination of two or moreselected from them. The hydrolyzates may be prepared by adding anaqueous basic solution such as an aqueous solution of sodium hydroxideor ammonia, or an aqueous acidic solution such as an aqueous solution ofhydrochloric acid, acetic acid or citric acid to the compound of formula(I) or (II), followed by stirring.

[0029] The hard coat film may contain metal oxide fine particles (incolloid form, for example). The metal oxide fine particles are notspecifically limited, and may be arbitrary selected from any particlesthat are known to be or may be found to be suitable for use in hard coatfilms for plastic lenses. Examples of the metal oxide fine particlesinclude fine particles of a single metal oxides such as aluminum oxide,titanium oxide, antimony oxide, tin oxide, zirconium oxide, siliconoxide, cerium oxide, iron oxide; as well as fine particles of acomposite oxide, for example, fine particles of a composite tinoxide-zirconium oxide-tungsten oxide as disclosed in JP-A-6-25603; fineparticles of a composite tin oxide-tungsten oxide as disclosed inJP-A-3-217230; fine particles of a composite metal oxide of titaniumoxide, cerium oxide and silicon oxide as disclosed in JP-A-8-113760;fine particles of a composite titanium oxide-zirconium oxide-tin oxideas disclosed in JP-A-10-306258; fine particles of a composite titaniumoxide-zirconium oxide-silicon oxide, and those of a composite stannicoxide-zirconium oxide-tungsten oxide as disclosed in JP-A-9-21901. Ofthese metal oxide fine particles known to be suitable for use in thisinvention, at least one type selected from silicon oxide fine particles,titanium oxide fine particles and tin oxide fine particles is preferred.

[0030] The mean particle size of the metal oxide fine particles may fallgenerally between 1 and 500 nm. These metal oxide fine particles may beused either singly or as a combination of two or more.

[0031] In the invention, the hard coat film is formed, for example, bycoating a plastic lens substrate with a coating composition. If desired,the coating composition may contain various organic solvents andsurfactants for improving the wettability of the substrate with thecomposition, thereby improving the surface smoothness of the hard coatfilm.

[0032] An organic solvent is optionally added to the coating compositionfor uniformly hydrolyzing the component in the composition and forcontrolling the degree of hydrolysis. Preferred examples of the organicsolvent include cellosolves such as methyl cellosolve, ethyl cellosolveand butyl cellosolve. More preferably for the organic solvent, such acellosolve is combined with any of isopropyl alcohol or butyl alcohol.In this case, the cellosolve content is preferably 3% by weight or more,more preferably 10% by weight or more. Further if desired, the coatingliquid for the hard coat film may contain a silicone surfactant forimproving the surface smoothness of the hard coat film formed of it. Inaddition, for improving the lightfastness of the hard coat film and forpreventing the film from deterioration, a UV absorbent, antioxidant,light stabilizer, antiaging agent and/or like agent may be added to thecoating composition to an extent that does not interfere with thephysical properties of the hard coat film formed on the lens surface.Thus prepared, the viscosity and solids content of the coating liquidare not specifically restricted, so far as it is advantageous applicableto coat the plastic lenses.

[0033] For applying the coating composition onto the surfaces of theplastic lens, an ordinary method such as dipping, spin coating, orspraying may be employed.

[0034] In order to provide high face accuracy of the film formed of thecomposition, especially preferred is dipping or spin coating. Thecomposition is cured by drying it in hot air or by exposing it to activeenergy rays. Preferably, it is cured in hot air at 70 to 200° C., morepreferably at 90 to 150° C. For the active energy rays, preferred arefar-infrared rays, which suppress damage of the film by heat in a lowdegree.

[0035] The plastic lenses to be processed in the invention are notspecifically limited, and examples thereof include, for example, methylmethacrylate homopolymers, copolymers of methyl methacrylate with atleast one other monomer, diethylene glycol bisallylcarbonatehomopolymers, copolymers of diethylene glycol bisallylcarbonate with atleast one other monomer, sulfur-containing copolymers,halogen-containing copolymers, polycarbonates, polystyrenes, polyvinylchlorides, unsaturated polyesters, polyethylene terephthalates,polyurethanes, and polythiourethanes.

[0036] In the method for producing the plastic lens of the invention,the hard coat film formed on the lens is coated with an aqueous liquidfilm which in turn is treated with ozone. Before the thus-treated hardcoat film is further coated with an antireflection film, it may beultrasonically rinsed in a tank and then washed with an alkali forremoving any impurities adhering thereto.

[0037] The inorganic oxide to be used in the invention for forming theantireflection film is not specifically limited and substances generallyknown for use as materials of ordinary antireflection films may be used.For example, they include Ta₂O₅, Y₂O₃, ZrO₂, SiO₂, TiO₂, Al₂O₃, andNb₂O₅. The antireflection film may be 0 formed by vapor deposition,which, however, may be combined with any suitable type of ionbeam-assisted deposition, sputtering or ion plating, if desired.

[0038] The antireflection film may be single-layered or multi-layered.In view of its reflectivity, adhesion to the underlying hard coat filmand abrasion resistance, it is preferable that the vapor depositionlayer of the antireflection film that is in contact with the hard coatfilm be formed mainly of silicon dioxide. When the antireflection filmis single-layered, its optical thickness is preferably 0.25λ₀(λ₀=450 to650 nm). For the antireflection film, also preferred are multi-layeredfilms, for example, a two-layered film of 0.25λ₀/0.25λ₀, in opticalthickness, in which the two layers differ in refractive index, or athree-layered film of 0.25λ₀/0.5λ₀/0.25λ₀ or 0.25λ₀/0.25λ₀/0.25λ₀ inoptical thickness in which the three layers differ in refractive index,or other multi-layered films that are partly substituted with any otherequivalent film.

[0039] If desired, an undercoat layer of, for example, a metal film ofniobium or a metal oxide film of silicon dioxide or aluminum oxide maybe disposed between the antireflection film and the hard coat filmformed of the coating composition according to the invention.

[0040] Also if desired, a primer film may be disposed between the hardcoat film and the plastic lens substrate, in order to improve the impactresistance of the coated lens and the adhesion of the hard coat film tothe lens substrate, for example, as disclosed in JP-A-3-109502. Oneexample of this primer film is an urethane film formed of apolyisocyanate and a polyol as raw materials. The polyisocyanateincludes, for example, adducts prepared by bonding a few molecules ofany of hexamethylene diisocyanate, 4,4′-cyclohexylmethane diisocyanateor hydrogenated xylylene diisocyanate by various methods; andisocyanurates, allophanates, biurets or carbodiimides blocked with anyof acetacetic acid, malonic acid or methyl ethyl ketoxime. The suitablepolyols include, for example, polyesters, polyethers, polycaprolactones,polycarbonates and polyacrylates having two or more hydroxyl groups inone molecule. Also if desired, the primer film may contain metal fineoxide particles such as titanium oxide fine particles for improving itsrefractivity.

[0041] The invention is described in more detail with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention. The physical properties of the samples inExamples and Comparative Examples were evaluated according to themethods mentioned below.

[0042] (a) Abrasion resistance: The plastic lenses with antireflectionfilm obtained in the Examples were dipped in warm water at 50° C. for 48hours, and then rubbed with 0000 steel wool (produced by Japan SteelWool Corp.) under a load of 1 kgf/cm² in the direction where the steelwool meets the lens surface at right angles. After rubbed 20 (back andforth) in that manner, the condition of each sample was evaluated forthe scratch resistance in accordance with the criteria mentioned below.

[0043] UA: Few scratches found.

[0044] A: Only a few scratches found.

[0045] B: Some scratches found.

[0046] C: Many scratches found.

[0047] (b) Adhesion: Each of the plastic lenses with antireflection filmobtained in the Examples were dipped in warm water at 50° C. for 48hours, and 10×10 cross-cuts of 1 mm square were cut into the surface ofthe hard coat film on the lens face. An adhesive tape of Cellophane(manufactured by Nichiban No. 405) was tightly stuck to each sample, andrapidly peeled off at a 90 degree angle. The number of cross-cutsremaining on each sample was counted.

[0048] (c) YI value: Before and after being treated with ozone, the hardcoat film of each sample was analyzed with a spectrometer U3410(manufactured by Hitachi Ltd., trade name). From the XYZ values of eachsample thus analyzed in the visual field of 20 the light source C, theYI value thereof was derived.

EXAMPLES 1 to 12, and COMPARATIVE EXAMPLES 1 to 5:

[0049] As set forth in Table 1, each plastic lens substrate (a) to (c)was coated with a hard coat film (A) to (C) and with an antireflectionfilm (α) to (γ). The concentration and the flow rate of the ozone gasused for treating the hard coat film, and the type and the flow rate ofthe processing water used for forming a liquid film on the hard coatfilm are shown in Table 1. Under these conditions, plastic lenses withantireflection film were produced. The details of the plastic lenssubstrates (a) to (c), the hard coat films (A) to (C), theantireflection films (α) to (γ), the method of treating the hard coatfilm with ozone gas and the method of forming the antireflection filmare mentioned below.

[0050] (1) Plastic lens substrate: The plastic lens substrates (a) to(c) used herein are as follows:

[0051] Plastic lens substrate (a): TESLALID (having a refractive indexof 1.71; trade name manufactured by Hoya—this is used in Example 1 andComparative Example 1).

[0052] Plastic lens substrate (b): EYAS (having a refractive index of1.60) (Trade name, manufactured by Hoya)—this is used in Examples 2 and3 and Comparative Example 2).

[0053] Plastic lens substrate (c): diethylene glycol bisallylcarbonatepolymer (having a refractive index of 1.499—this is used in Examples 4to 12 and Comparative Examples 3 to 5).

[0054] (2) Preparation of hard coat liquid and formation of hard coatfilm: Hard coat films (A) to (C) mentioned below were formed.

Preparation of Hard Coat Liquid (A), and Formation of Hard Coat Film ofit (The Hard Coat Film Contains Composite Fine Particles of TitaniumOxide, Zirconium Oxide and Silicon Oxide: This is Formed in Example 1and Comparative Example 1):

[0055] 1045 parts by weight of γ-glycidoxypropyl(trimethoxy)silane and200 parts by weight of γ-glycidoxypropylmethyl(diethoxy)silane were putinto a stainless reactor, and 299 parts by weight of hydrochloric acid(0.01 mols/liter) were added thereto with stirring. The stirring wascontinued for one full day in a clean room at 10° C. to obtain a silanehydrolyzate.

[0056] In another reactor, 4018 parts by weight of methyl cellosolve and830 parts by weight of isopropanol were added to and mixed with 3998parts by weight of a composite fine particle sol of titanium oxide,zirconium oxide and silicon oxide (dispersed in methanol, having a totalsolid content of 30% by weight and having a mean particle size of from 5to 8 microns) with stirring, and 4 parts by weight of a siliconesurfactant (manufactured by Nippon Unicar L-7001) and 100 parts byweight of aluminum acetylacetonate were added thereto. Like thehydrolyzate discussed above, it was stirred for one full day in a cleanroom at 10° C., and then this was combined with the hydrolyzate andfurther stirred for one full day. Thereafter, this was filtered througha 3-μm filter to obtain a hard coat liquid (A).

[0057] Next, the plastic lens was dipped in the hard coat liquid (A) for20 seconds, pulled up at a pulling rate of 20 cm/min, and then heated inan oven set at 110° C. for 1 hour. Thus processed, the plastic lens wascoated with a hard coat film (A).

Preparation of Hard Coat Liquid (B), and Formation of Hard Coat Film ofit (The Hard Coat Film Contains Composite Fine Particles of StannicOxide-Zirconium Oxide: This is Formed in Examples 2 and 3 andComparative Example 2):

[0058] b 142 parts by weight of γ-glycidoxypropyltrimethoxysilane wereput into a glass reactor equipped with a magnetic stirrer, and 1.4 partsby weight of 0.01 N hydrochloric acid and 32 parts by weight of waterwere added dropwise thereto with stirring. This was then stirred for 24hours to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.Next, 460 parts by weight of stannic oxide-zirconium oxide compositefine particles (dispersed in methanol, having a total metal oxidecontent of 31.5% by weight and having a mean particle size of from 10 to15 millimicrons), 300 parts by weight of ethyl cellosolve, 0.7 parts byweight of a silicone surfactant serving as a lubricant, and 8 parts byweight of a curing agent, aluminum acetyl acetonate were added to theγ-glycidoxypropyltrimethoxysilane hydrolyzate, well stirred, and thenfiltered to obtain a hard coat liquid (B).

[0059] Next, the plastic lens was dipped in an aqueous alkali solutionand washed well. Then, this was dipped in the hard coat liquid (B),pulled up at a pulling rate of 14 cm/min, and heated in an oven set at120° C. for 1 hour. Thus processed, the plastic lens was coated with ahard coat film (13).

Preparation of Hard Coat Liquid (C), and Formation of Hard Coat Film ofit (The Hard Coat Film Contains Silicon Oxide Fine Particles, This isFormed in Examples 4 to 12 and Comparative Examples 3 to 5):

[0060] 120 parts by weight of γ-glycidoxypropyltrimethoxysilane were putinto a glass reactor equipped with a magnetic stirrer, and 27 parts byweight of 0.1 N hydrochloric acid were added dropwise thereto withstirring. This was then stirred for 24 hours to obtain a hydrolyzate ofthe silane. Next, 200 parts by weight of water-dispersed silica fineparticles (having a solid content of 20% and having a mean particle sizeof 15 millimicrons), 100 parts by weight of isopropyl alcohol and 100parts by weight of ethyl cellosolve both serving as a solvent, 1 part byweight of a silicone surfactant serving as a lubricant, and 7 parts byweight of a curing agent, aluminum acetylacetonate were added to thehydrolyzate, stirred well, and then filtered to obtain a hard coatliquid (C).

[0061] Next, the plastic lens was dipped in an aqueous alkali solutionand washed well. Then, this was dipped in the hard coat liquid (C),pulled up at a pulling rate of 14 cm/min, and heated in an oven set at120° C. for 1 hour. Thus processed, the plastic lens was coated with ahard coat film (C).

[0062] (3) Treatment with ozone gas: The ozone gas-treating apparatus ofFIGS. 1 and 2 was used. For the solution in the solution pool 3 b in thetreating tank 3 shown in FIGS. 1 and 2, pure water (in Examples 1, 2 and6) or a solution of sodium hydrogen carbonate of 0.05 mols/liter to 0.2mols/liter (in Examples 3 to 5, and 7 to 12) was used. The concentrationof ozone flowing through the ejection tube 8 in FIG. 2 was from 70 to180 g/Nm³. The ozone gas flow rate through the ejection tube 8 in FIG. 2was from 2.5 to 2.7 liters/min, and the spray ejected out of the spraynozzle 10 to form a liquid film on the hard coat film was from 2 to 2.6liters/min, as in Table 1. The volume of the space in the treating tank3 was 118 liters (430×430×640 mm). The solution temperature in thesolution pool 3 b was between 19° C. and 25° C.; and the ozone gastemperature fell between 21° C. and 36° C.

[0063] (4) Washing after treatment with ozone gas: After being treatedwith ozone gas, the plastic lens was dipped in warm water (pure water offrom 1 to 10 μs/cm, at 55° C.) for 30 seconds for rinsing, and then inan alkali solution (containing 0.3% anionic surfactant) at 48° C. for 75seconds for removing any impurities adhering to the hard coat film.

[0064] (5) Formation of antireflection film: After the treatment withozone gas and washing as in (4), each plastic lens was coated with anyof the following three antireflection films.

Formation of Antireflection Film (c) (in Example 1 and ComparativeExample 1):

[0065] Evaporating materials were deposited through vacuum evaporationon the hard coat film of each plastic lens to form thereby a 7-layeredantireflection film of SiO₂(0.125 λ)/Ta₂O₅(0.05 λ)/SiO₂(0.5λ)/Ta₂O₅(0.125 λ)/SiO₂(0.05 λ)/Ta₂O₅(0.25λ)/SiO₂(0.25 λ) on the hardcoat layer in that order. In this, λ is 500 nm.

Formation of Antireflection Film (β) (in Examples 2 and 3, andComparative Example 2):

[0066] SiO₂¾ λ thick was deposited on the hard coat film of each plasticlens through vacuum evaporation to be a first layer. On the other hand,Nb₂O₅ powder, ZrO₂ powder and Y₂O₃ powder were mixed, shaped underpressure and sintered to prepare an evaporating composition. This wasdeposited on the first layer along with SiO₂ to form thereon a compositelayer {fraction (1/4)} λ thick. Next, another composite layer ofevaporating composition/SiO₂¼ λ evaporating composition {fraction (1/2)}λ thick was deposited thereon; and finally SiO₂¼ λ thick was depositedthereon to form a multi-layered antireflection film on the hard coatlayer. In this, λ is 500 nm.

Formation of Antireflection Film (γ) (in Examples 4 to 12 andComparative Examples 3 to 5):

[0067] SiO₂{fraction (6/4)} λ thick was deposited on the hard coat filmof each plastic lens through vacuum evaporation to be a first layer.With that, ZrO₂ about {fraction (1/17)} λ thick was deposited thereon,and then SiO₂ was thereon to form a second layer of SiO₂ and ZrO₂ havingan overall thickness of λ/4. Further, ZrO₂ about ½ λ thick was depositedthereon to be a third layer; and finally SiO₂¼ λ thick was thereon tocomplete a multi-layered antireflection film on the hard coat film. Inthis, λ is 500 nm.

[0068] The coated plastic lens samples of Examples 4 to 12 had the samesubstrate, hard coat film and composition of the antireflection film,but differed with respect to the processing water, the processing timeand the ozone concentration in treating the hard coat film of eachsample.

[0069] In Comparative Example 1, the same substrate as in Example 1 wascoated with the same hard coat film, but this was directly washed as inExample 1, without being coated with a liquid film or treated with ozonegas, and thereafter this was coated with the same antireflection film asin Example 1.

[0070] In Comparative Example 2, the same substrate as in Example 2 wascoated with the same hard coat film, but this was directly washed as inExample 2, without being coated with a liquid film or treated with ozonegas, and thereafter this was coated with the same antireflection film asin Example 2.

[0071] In Comparative Example 3, the same substrate as in Examples 4 to12 was coated with the same hard coat film, but this was directly washedas in Examples 4 to 12, without being coated with a liquid film nortreated with ozone gas, and thereafter this was coated with the sameantireflection film as in Examples 4 to 12.

[0072] In Comparative Example 4, the same substrate as in Examples 4 to12 was coated with the same hard coat film, and this was, after beingtreated with ozone gas alone (at 15 to 40° C.) but not coated with aliquid film prior to the treatment, washed as in Examples 4 to 12, andthereafter this was coated with the same antireflection film as inExamples 4 to 12.

[0073] In Comparative Example 5, the same substrate as in Examples 4 to12 was coated with the same hard coat film, and this was, after beingdipped in ozone water (at 15 to 40° C.) but not coated with a liquidfilm prior to the dipping, washed as in Examples 4 to 12, and thereafterthis was coated with the same antireflection film as in Examples 4 to12.

[0074] The plastic lenses obtained in Examples 1 to 12 and ComparativeExamples 1 to 5 were tested according to test methods (a) to (c)mentioned above. The results are given in Table 2. TABLE 1 Plas- ticOzone Lens Hard Antire- Ozone Ozone Gas Gas Solution Flow Sub- Coatflection Method of Ozone Gas Treating Concentration Flow Rate Solutionfor Liquid Film Rate strate Film Film Treatment Time (sec) (g/Nm³)(liter/min) Formation (liter/min) (liter/min) Examples 1 a A α waterspray + ozone gas 60 145 2.7 pure water 2 2 b B β water spray + ozonegas 60 140 2.5 pure water 2.5 3 b B β water spray + ozone gas 60 140 2.50.2 mols/liter NaHCO₃ 2.5 4 c C γ water spray + ozone gas 60 140 2.6 0.2mols/liter NaHCO₃ 2.1 5 c C γ water spray + ozone gas 240 140 2.7 0.1mols/liter NaHCO₃ 2.3 6 c C γ water spray + ozone gas 60 140 2.7 purewater 2.6 7 c C γ water spray + ozone gas 30 125 2.7 0.2mols/literNaHCO₃ 2.6 8 c C γ water spray + ozone gas 30 150 2.7 0.05mols/liter NaHCO₃ 2.2 9 c C γ water spray + ozone gas 300 140 2.7 0.05mols/liter NaHCO₃ 2.4 10 c C γ water spray + ozone gas 120 180 2.7 0.2mols/liter NaHCO₃ 2.4 11 c C γ water spray + ozone gas 120 70 2.4 0.2mols/liter NaHCO₃ 2.5 12 c C γ water spray + ozone gas 120 110 2.4 0.2mols/liter NaHCO₃ 2.5 Comp. Examples 1 a A α No — — — — — 2 b B β No — —— — — 3 c C γ No — — — — — 4 c C γ ozone gas 60 120 2.7 — — 5 c C γdipping in ozone water 600 140 2.7 pure water 0

[0075] TABLE 2 Adhesion after accelerated Abrasion aging YI Value YIValue Resistance (Adhesion before after after after ozone ozonetreatment treatment treatment treatment in warm in warm (hard coat (hardcoat water water) lenses) lenses) Examples  1 A 100 2.18 2.18  2 UA 1001.05 1.05  3 UA 100 1.05 1.05  4 UA 100 0.81 0.80  5 UA 100 0.81 0.81  6UA 100 0.81 0.82  7 UA 100 0.80 0.80  8 UA 100 0.82 0.81  9 UA 100 0.810.82 10 UA 100 0.81 0.80 11 UA 100 0.82 0.82 12 UA 100 0.81 0.82Comparative Examples  1 C 0 2.18 —  2 A 98 1.05 —  3 UA 0 0.81 —  4 UA90 0.81 0.82  5 UA 50 0.81 0.81

What is claimed is:
 1. A method for producing a plastic lens with anantireflection film on a surface thereof, comprising: applying water oran aqueous solution to a plastic lens having an organosiliconcompound-containing hard coat film formed on a surface thereof to form aliquid film of water or the aqueous solution on the surface of the hardcoat film, allowing ozone gas to contact with the liquid film so as totreat the surface of the hard coat film with the ozone gas, and formingthe antireflection film on the ozone gas treated surface of the hardcoat film by vapor deposition.
 2. The method for producing a plasticlens with an antireflection film of claim 1, comprising spraying thewater or the aqueous solution on the hard coat-film to form the liquidfilm on the hard coat film.
 3. The method for producing a plastic lenswith an antireflection film of claim 1, wherein the water or the aqueoussolution further comprises ozone gas.
 4. The method for producing aplastic lens with an antireflection film of claims 1, 2 or 3, whereinthe aqueous solution contains a radical scavenger.
 5. The method forproducing a plastic lens with an antireflection film of claim 4, whereinthe radical scavenger is a hydrogen carbonate or a phosphate.
 6. Themethod for producing a plastic lens with an antireflection film of claim5, wherein the aqueous solution contains the radical scavenger in anamount of 0.01 mols/liter or more based on the aqueous solution.
 7. Themethod for producing a plastic lens of claim 1, wherein the hard coatfilm contains metal oxide fine particles.
 8. The method for producing aplastic lens of claim 7, wherein the metal oxide fine particles compriseat least one type of particle selected from silicon oxide particles,titanium oxide particles and tin oxide particles.
 9. The method forproducing a plastic lens of claim 1, wherein the plastic lens comprisesat least one resin selected from the group consisting of apolythiourethane resin, an epithio group-containing resin and adiethylene glycol bisallylcarbonate-containing resin.
 10. The method forproducing a plastic lens of 1, wherein the concentration of the ozonegas allowed to contact the liquid film on the hard coat film is 50 g/Nm³or more.
 11. The method for producing a plastic lens of claim 1, whereinthe concentration of the ozone gas allowed to contact the liquid film onthe hard coat film is 100 g/Nm³ or more.
 12. The method for producing aplastic lens of claim 1, wherein the concentration of the ozone gasallowed to contact the liquid film on the hard coat film is 140 g/Nm³ ormore.
 13. The method for producing a plastic lens as claimed in claim 1,2, 3, 7, 8, 9, 10, 11 or 12, wherein the time for contacting the ozonegas with the liquid film is between about 10 seconds and about 10minutes.
 14. The method for producing a plastic lens as claimed in claim4, wherein the time for contacting the ozone gas with the liquid film isbetween about 10 seconds and about 10 minutes.
 15. The method forproducing a plastic lens as claimed in claim 5, wherein the time forcontacting the ozone gas with the liquid film is between about 10seconds and about 10 minutes.
 16. The method for producing a plasticlens as claimed in claim 6, wherein the time for contacting the ozonegas with the liquid film is between about 10 seconds and about 10minutes.
 17. The method for producing a plastic lens as claimed in claim1, 2, 3, 7, 8, 9, 10, 11 or 12, wherein the organosilicon compound usedto form the hard coat film is at least one compound selected fromcompounds of general formula (I): (R¹)_(a)(R³)_(b)Si(OR²)_(4−(a+b))  (I) wherein R¹ and R³ each independently represent a monovalenthydrocarbon group having from 1 to 10 carbon atoms, with or without afunctional group; R² represents an alkyl group having from 1 to 8 carbonatoms, an aryl group having from 6 to 10 carbon atoms, an aralkyl grouphaving from 7 to 10 carbon atoms or an acyl group having from 1 to 8carbon atoms; a and b each independently indicate 0 or 1; and aplurality of the OR² groups may be the same or different from eachother, and compounds of general formula (II):

wherein R⁴ and R⁵ each independently represent a monovalent hydrocarbongroup having from 1 to 5 carbon atoms, with or without a functionalgroup; X¹ and X² each independently represent an alkyl group having from1 to 4 carbon atoms or an acyl group having from 1 to 4 carbon atoms; Yrepresents a divalent hydrocarbon group having from 1 to 20 carbonatoms; x and y each independently indicate 0 or 1; a plurality of the X¹groups may be the same or different from each other; and a plurality ofthe X² groups may be the same or different from each other, andhydrolyzates of the compounds of formula (I) and formula (II).
 18. Themethod for producing a plastic lens as claimed in claim 4, wherein theorganosilicon compound used to form the hard coat film is at least onecompound selected from compounds of general formula (I):(R¹)_(a)(R³)_(b)Si(OR²)_(4−(a+b))   (I) wherein R¹ and R³ eachindependently represent a monovalent hydrocarbon group having from 1 to10 carbon atoms, with or without a functional group; R² represents analkyl group having from 1 to 8 carbon atoms, an aryl group having from 6to 10 carbon atoms, an aralkyl group having from 7 to 10 carbon atoms oran acyl group having from 1 to 8 carbon atoms; a and b eachindependently indicate 0 or 1; and a plurality of the OR² groups may bethe same or different from each other,

and compounds of general formula (II): wherein R⁴ and R⁵ eachindependently represent a monovalent hydrocarbon group having from 1 to5 carbon atoms, with or without a functional group; X¹ and X² eachindependently represent an alkyl group having from 1 to 4 carbon atomsor an acyl group having from 1 to 4 carbon atoms; Y represents adivalent hydrocarbon group having from 1 to 20 carbon atoms; x and yeach independently indicate 0 or 1; a plurality of the X¹ groups may bethe same or different from each other; and a plurality of the X² groupsmay be the same or different from each other, and hydrolyzates of thecompounds of formula (I) and formula (II).
 19. A plastic lens with anantireflection film produced by the method of claim
 13. 20. A plasticlens with an antireflection film produced by the method of claim 15.